Direct-dyeing cupriferous disazo-



United States Patent 2,832,763 DlRECT-DYEING CUPRIFEROUS DISAZO- DYESTUFFS Henri Riat, Arlesheirn, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm N 0 Drawing. Application May 16, 1955 Serial No. 508,817

Claims priority, application Switzerland May 31, 1954 8 Claims. (Cl. 260-148) 2,832,?63 Patented Apr.-

The present invention relates to new cupriferous disazo- 10 the formula (20) 0-CnHIm-Ho n dyestufls which, like for example the dyestufi of the formula HOsS- correspond to the general formula wherein Y and Y each represent a hydroxyl group, at least one of which groups is etherified by an aliphatic radical, advantageously an aliphatic radical containing up to four carbon atoms which may contain, in addition to the carbon and hydrogen atoms only oxygen atoms with single bonds. Thus in the above formula 2Y may represent an alkoxy group advantageously of low molecular in which m, n, p and q each represents a whole number, m having a value of at least 2 and at the most 4, p having a value of at least 1 and-at the most 5, q having a is at the most that of the carbon atoms in such radical minus one.

The new cupriferous disazo dyestufis are obtained by Weight, which may preferably be further substituted by at treating a disazo-dyestufi of the formula least one hydroxyl or alkylated hydroxyl group, and Y; represents a group corresponding to the definition of Y or a hydroxyl group.

More particularly the new cupriferous dyestutfs may correspond to the formula OH H10 0 O CH: H O Y;

803E HOsB- SOsH wherein Y represents an alkoxy group advantageously of low molecular weight, which may preferably be further substituted by hydroxyl or alkylated hydroxyl groups, and Y, represents an alkoxy group corresponding to the definition of Y; or a hydroxyl group, with an agent yielding copper complexes are formed with the splitting off of the methoxy groups.

The disazo-dyestuffs of the Formula 3 used as starting materials in the present process can be prepared by coupling a tetrazo-compound of the dianisi'dine of theformula (4 H300 ooHa HaN on both sides with an azo-component of the formula HO=S- $0331 oron one side with such an ago-component and on the other side with an ale-component of the formula (6) HO Y2 (in the Formulae 5 and 6 Y and Y having the meanings given above).

The alkoxy group Y or Y respectively in the amcomponents of the Formulae 5 and 6 canbe one with a saturated or unsaturated, aliphatic hydrocarbon radical. These alkoxy groups, such as for instance the methoxy-, ethoxy-, n-propyloxy-, isopropyloxyor allyloxy groups, can be free from further substituents.

Those dyestuffs of the Formula 2 mentioned above are however preferable in which at least one of the a ksarswup X1 o sis, fu t er s bs tu d in a .hydroxyl group which may be alkylated or especially by an HO-group. As a rule, it is of advantage to use azocomponents of the Formula 5 with such alkoxy groups whose alkyl radicals, which may be further substituted in the aforementioned manner, only contain few, for example 1 to 4 carbon atoms. Valuable results are obtained for example with aZo-components of the kind described whose alkoxy groups are substituted in the a ky r di a sby its 2 hysl o y o p 1F r h ted eth .tadis l gen a v ta eousl h at the formula wherein n represents either 1 or 2.

By coupling tetrazo-compounds of the kind described with two different axe-components of the Formula 5, asymmetrical dyestufis are obtained. As can be seen above, the tetrazo-comp'ound can in this case also be coupled on the one side with an azo-component of the Formula 5 and ,on the other side with 1:8-.d ihydroxynaphthalene-3:6-disulfonic acid. In the manufactureof asynmietrical dyestufis it is also especially advantageous at leas n o t az -wmnone u hasa al pay radica further substituted by a further allgoxy group or advantageously by at least one hydroxyl group.

As examples of suitable s ze-components the followns c mp un ay be men ioned:

l-methoxyor 1-ethoxy-8-hydroxynaphthalene-3:6-disulfonic acid,

1 9 hydroxyethoxy 8 hydroxynaphthalene 3 :6 disulfonic acid,

l-isopropyloxyor isobutyloxy 8 hydroxynaphthalene-,

3:6-disulfonic acid, l-pw-dihydroxypropyloxy 8 hydroxynaphthalene-figodisulfonic acid,

' the Formula 2 defined above.

4 1-5- or -'y-hydroxypropyloxy-8-hydroxynaphthalene-3:6-

disulfonic acid, 1-n-propyloxy-8-hydroxynaphthalene-3 G-disnlfonic acid, 1-allyloxy-8-hydroxynaphthalene-3 6-disulfonic acid, l 5 methoxy-ethoxy 8 hydroxynaphthalene-3:6-disulfonic acid.

The azo-components of the Formula 5 can be obtained by known methods, for example by alkylating 1:8- dihydroxynaphthalene 3 :6 disulfonic acid. The l-hydroxy-alkoxy-8-hydroxynaphthalene-3 zo-disulfonic acids can be for example prepared advantageously by reacting 1: 8&dihydroxynaphthalene-3:6-disulfonic acid with hydroxyalkyl halides or alkylene oxides, such as for instance ethylene oxide, preferably in an aqueous medium and in the presence of an acid-binding agent.

The coupling of the tetrazotized 3:3'-dimethoxy-4:4- diamino-diphenyl with the ale-components of the Formulae 5 and 6 can also be carried out by known methods, advantageously in an alkaline medium, for example in a medium rendered alkaline with alkali carbonate. The couplings can be facilitated by suitable adjuvants, such as alcohol or pyridine.

The treatment with the agents yielding copper can also be carried out by known methods. It should be carried out in such a way that bis-(ortho:ort ho-d ihydroxy-azo)-copper complexes are formed. It is advisable to carry out the metallization with complex copper amine compounds, for instance copper tetramine compounds from ammonia, pyridine, alkylamines or more especially hydroxyethylamines.

The cupriferous dyestutfs so obtained correspond to This formula as Well as the other formulae of cupriferous dyestufis as presented herein undoubtedly shows the right stoichiometn'c quantity of copper and the correct position of the copper atom in the complex, whereas the distribution of the principal and secondary valencies in the complex linkage of the copper to the dyestufi is not yet absolutely definite.

The new cupriferous dyestuffs of the Formula 2 are suitable for the dyeing and printing of various materials, especially cellulosic fibers, such as cotton, linen, artificial silk or staple fibers from regenerated cellulose. The dyeings are distinguished by good fastness to light and, as a rule, also by other good fastness properties, such as for example a relatively good tastness to brightening, acid and perspiration. The new dyestufis are also especially valuable because generally extremely pure, blue tints are obtained, the production of which has up to the present not been possible with the known dyestuffs of the same type. The, tints also remain good in artificial light. Viscose artificial silk showing a tendency to dye streakily is dyed uniformly with the new dyestuifs.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated.

Example 1 paste is dissolved in 2500 parts of water, and 50 parts of monoethanolarnine are added. A solution of 55 parts of crystalline copper sulfate, parts of ammonia of 25% strength and partsof water is then added and the whole heated under reflux for 24 hours with stirring on a boiling water bath. The copper complex formed is then salted out by adding sodium chloride, filtered oif 8-hydroxynaphthalene-3:6 disulfonic acid is replaced by and dried. The dyestutf is a dark powder which dissolves 1-5-methoxy-ethoxy-8-hydroxynaphthalene-3: fi-disulfonic in water with a blue color and dyes cotton clear greenacid or l-B-hydroxypropyl-8-hydroxynaphthalene-3:6-diish blue tints. sulfonic acid.

The 1-fi-hydroxyethoxy-8-hydr0xynaphthalene-3: 6-di- E I 3 sulfonic acid used in the example is obtained by reacting xamp e ethylene chlorhydrin (about 1.5 mols) with1z8-dihydroxy- 100 parts of cotton are entered at 40 C.-into a dyenaphthalene-3:6-disulfonic acid (1 mol) in an aqueous bath containing 0.8 part of the cupriferous dyestuff desolution and in the presence of calcium carbonate at boilscribed in the first and second paragraphs of Example 1 ing temperature. 10 in 3000 parts of water. Dyeing is carried on for half A dyestuif which also dyes cotton blue tints is obtained an hour while raising the temperature to 90 C., 30 parts when 1-,8-hydroxyethoxy-8-hydroxynaphthalene-3:6-disulof crystalline sodium sulfate are added and dyeing is fonic acid is replaced by l-ethoxy-S-hydroxynaphthalenecontinued for another half hour at 90 to 95 C. The 3:6-disulfonic acid. cotton is then rinsed and the operation finished in the Further dyestuffs having similar properties to the comusual manner. There is obtained a pure greenish blue plex copper compound obtained according to paragraphs dyeing which is fast to light.

1 and 2 of the present example are obtained by using What is claimed is: instead of 1--hydroxyethoxy-8-hydroxynaphthalene-3:6- 1. A cupriferous disazo dyestutf of the formula disulfonic acid an equivalent quantity of l-fior -'y-hydroxypropyloxy-8-hydroxynaphthalene-3:6-disulfonic acid m whlch p and q each represents a Whole number m having a value of at least 2 and at the most 4, p havg i 'f ig'i gg ing a value of at least 1 and at the most 5, q having a value of at least 2, and wherein the number of oxygen Examp 1e 2 atoms of each of the radicals -C H O, and 24.4 parts of 3:3'-dimethoxy-4:4'-diaminodiphenyl H O is at the most that of the carbon atoms are tetrazotized in the usual manner, and the tetrazoin such radical minus one. compound is mixed with a solution of 32 parts of 1:8- 2. A cupiferous disazo dyestutf of the formula Y1 O-Cu0 O-Ou0 Y:

110,8 SOIH HOsS- 03H dihydroxynaphthalene-3:fi-disulfonic acid rendered a'lkain which Y and Y each represents a hydroxyalkoxy line with sodium carbonate. As soon as no more of the group containing at the most three carbon atoms. tetrazo-compound can be detected, a solution of 37 parts 3. A cupriferous disazo dyestutf of the formula of l-fl-hydroxyethoxy-S -hydroxynaphthalene-3:6-disulin which Y and Y each represents a hydroxyalkoxy fonic acid and parts of pyridine is added and the whole group containing at the most three carbon atoms and a is stirred until coupling is complete, the coupling mixture single hydroxyl group.

being kept alkaline by the addition of sodium carbonate. 4. A cupriferous disazo dyestutf of the formula Y; 0 Cu-O o-cuo 0H N=N- N=N' HO:S- SOaH HOJS S0aH The disazo-dyestufi is salted out, filtered and converted in which Y represents a hydroxyl group containing at into the copper complex according to the method dethe most three carbon atoms.

scribed in Example 1. After working up, a powder is 5. A cupriferous disazo dyestufl? of the formula Y1 0 Cu-0 ?-Cu-O OH H0:S 802B 110:8 -SO:H

obtained which dissolves in water with a blue color and in which Y represents a hydroxyalkyl group containing dyes cotton greenish blue tints. at the most three carbon atoms and a single hydroxyl A similar dyestuff is obtained when l-fl-hydroxyethoxygroup.

7. The cupriferous disazo-dyestufi of the formula HO-HC-HzC-O 0-0u-0 o References Cited in the file of this patent UNITED STATES PATENTS 1,921,337 Wiedemann et a1. Aug. 8, 1933 2,476,260 Mayer et a1. July 12, 1949 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,832,763 April 29, 1958 Henri Riat It is hereby certified that error appears in the printed specification of tlie above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, line 63, for hydroiryl" read hydroxyalkyl Signed and sealed this 21st day of October 1958.,

(SEAL) Attest:

KARL H. .AXLINE ROBERT C. WATSON Attesting Ofiicer Commissioner of Patents 

1. A CUPRIFEROUS DISAZO DYESTUFF OF THE FORMULA 